Study of Beryllium, Magnesium, and Spodium Bonds to Carbenes and Carbodiphosphoranes

The aim of this article is to present results of theoretical study on the properties of C⋯M bonds, where C is either a carbene or carbodiphosphorane carbon atom and M is an acidic center of MX2 (M = Be, Mg, Zn). Due to the rarity of theoretical data regarding the C⋯Zn bond (i.e., the zinc bond), the main focus is placed on comparing the characteristics of this interaction with C⋯Be (beryllium bond) and C⋯Mg (magnesium bond). For this purpose, theoretical studies (ωB97X-D/6-311++G(2df,2p)) have been performed for a large group of dimers formed by MX2 (X = H, F, Cl, Br, Me) and either a carbene ((NH2)2C, imidazol-2-ylidene, imidazolidin-2-ylidene, tetrahydropyrymid-2-ylidene, cyclopropenylidene) or carbodiphosphorane ((PH3)2C, (NH3)2C) molecule. The investigated dimers are characterized by a very strong charge transfer effect from either the carbene or carbodiphosphorane molecule to the MX2 one. This may even be over six times as strong as in the water dimer. According to the QTAIM and NCI method, the zinc bond is not very different than the beryllium bond, with both featuring a significant covalent contribution. However, the zinc bond should be definitely stronger if delocalization index is considered.

Through-Bond and Through-Space Interactions in [2,2]Cyclophanes

The interpretation of the distortions of the electron distribution in [2,2]cyclophanes (22-CPs) is controversial. Some studies indicate that there is an accumulation of electron density (ρ) outside the cavity of 22-CPs. The nature of through-space (ts) interaction is still under debate. The relative importance of ts and through-bond (tb) is an open question. In an attempt to clarify these points, we have investigated five 22-CPs and their corresponding toluene dimers by molecular orbitals analysis, electron density difference analysis, some topological analysis of ρ (quantum theory of atoms in molecules (QTAIM), electron localization function (ELF) and noncovalent interactions (NCI)), and energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV). ρ is concentrated inside the inter-ring region. All the analyses indicated that ts is predominant. The ts is composed by attractive dispersion and Pauli repulsion, with a small covalent contribution. Except for 1 and 6, all the compounds present inter-ring bond paths.

Analysis of charge density in nonaaquagadolinium(III) trifluoromethanesulfonate – insight into GdIII—OH2 bonding

The experimental charge-density distribution in [Gd(H2O)9](CF3SO3)3 has been analysed and compared with the theoretical density functional theory calculations. Although the Gd—OH2 bonds are mainly ionic, a covalent contribution is detectable when inspecting both the topological parameters of these bonds and the natural bond orbital results. This contribution originates from small electron transfer from the lone pairs of oxygen atoms to empty 5d and 6s spin orbitals of Gd3+.

Mapping C−H•••M interactions in confined spaces: (α-ICyDᴹᵉ)Au, Ag, Cu complexes reveal “contra-electrostatic H-bonds” masquerading as anagostic interactions

<p>What happens when a C−H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as “contra-electrostatic” H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. While electrostatics is strongly stabilizing component in the conventional C−H<b>•••</b>X bonds where X is an electronegative main group element, it is destabilizing in the C−H<b>•••</b>M contacts when M is Au(I), Ag(I), or Cu(I) of NHC−M−Cl systems. Such remarkable C−H<b>•••</b>M interaction became experimentally accessible within (α-ICyD^Me)MCl, NHC−Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C−H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of <i>d</i>-orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C−H bond to point toward the metal, and reveals a still attractive “contra-electrostatic” H-bonding interaction.</p>

Mapping C−H•••M interactions in confined spaces: (α-ICyDᴹᵉ)Au, Ag, Cu complexes reveal “contra-electrostatic H-bonds” masquerading as anagostic interactions

<p>What happens when a C−H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as “contra-electrostatic” H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. While electrostatics is strongly stabilizing component in the conventional C−H<b>•••</b>X bonds where X is an electronegative main group element, it is destabilizing in the C−H<b>•••</b>M contacts when M is Au(I), Ag(I), or Cu(I) of NHC−M−Cl systems. Such remarkable C−H<b>•••</b>M interaction became experimentally accessible within (α-ICyD^Me)MCl, NHC−Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C−H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of <i>d</i>-orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C−H bond to point toward the metal, and reveals a still attractive “contra-electrostatic” H-bonding interaction.</p>

Mapping the coordination space for C−H•••M interactions in confined spaces: (α-ICyDᴹᵉ)Au, Ag, Cu complexes reveal “contra-electrostatic H-bonds” masquerading as anagostic interactions

<p><b>Abstract: </b>What happens when a C−H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as “contra-electrostatic” H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. Whereas electrostatics is strongly stabilizing in the conventional C−H•••X bonds where X is an electronegative main group element, it is destabilizing in the C−H•••M contacts when M is Au(I), Ag(I), or Cu(I) of NHC−M−Cl systems. Such remarkable C−H•••M interaction became experimentally accessible within (a-ICyD^Me)MCl, NHC−Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C−H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of <i>d</i>-orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C−H bond to point toward the metal, and reveals a still attractive “contra-electrostatic” H-bonding interaction.</p>

Tetrel Interactions from an Interacting Quantum Atoms Perspective

Tetrel bonds, the purportedly non-covalent interaction between a molecule that contains an atom of group 14 and an anion or (more generally) an atom or molecule with lone electron pairs, are under intense scrutiny. In this work, we perform an interacting quantum atoms (IQA) analysis of several simple complexes formed between an electrophilic fragment (A) (CH3F, CH4, CO2, CS2, SiO2, SiH3F, SiH4, GeH3F, GeO2, and GeH4) and an electron-pair-rich system (B) (NCH, NCO-, OCN-, F-, Br-, CN-, CO, CS, Kr, NC-, NH3, OC, OH2, SH-, and N3-) at the aug-cc-pvtz coupled cluster singles and doubles (CCSD) level of calculation. The binding energy ( E bind AB ) is separated into intrafragment and inter-fragment components, and the latter in turn split into classical and covalent contributions. It is shown that the three terms are important in determining E bind AB , with absolute values that increase in passing from electrophilic fragments containing C, Ge, and Si. The degree of covalency between A and B is measured through the real space bond order known as the delocalization index ( δ AB ). Finally, a good linear correlation is found between δ AB and E xc AB , the exchange correlation (xc) or covalent contribution to E bind AB .

Towards understanding π-stacking interactions between non-aromatic rings

The first systematic study of π interactions between non-aromatic rings, based on the authors' own results from an experimental X-ray charge-density analysis assisted by quantum chemical calculations, is presented. The landmark (non-aromatic) examples include quinoid rings, planar radicals and metal-chelate rings. The results can be summarized as: (i) non-aromatic planar polyenic rings can be stacked, (ii) interactions are more pronounced between systems or rings with little or no π-electron delocalization (e.g. quinones) than those involving delocalized systems (e.g. aromatics), and (iii) the main component of the interaction is electrostatic/multipolar between closed-shell rings, whereas (iv) interactions between radicals involve a significant covalent contribution (multicentric bonding). Thus, stacking covers a wide range of interactions and energies, ranging from weak dispersion to unlocalized two-electron multicentric covalent bonding (`pancake bonding'), allowing a face-to-face stacking arrangement in some chemical species (quinone anions). The predominant interaction in a particular stacked system modulates the physical properties and defines a strategy for crystal engineering of functional materials.

Covalency and magnetic anisotropy in lanthanide single molecule magnets: the DyDOTA archetype

The unexpected covalent contribution in the DOTADy-OH2 bond revealed by ab initio calculations of the easy axis of magnetization through simple H2O rotations.

Red photo- and electroluminescent half-lantern cyclometalated dinuclear platinum(II) complex

New cyclometalated dinuclear platinum(II) complex bearing bridged 4,6-dimethylpyrimidine-2(1H)-thiolate (μ-C6H7N2S-κN,S) ligands, [{Pt(ppy)(μ-C6H7N2S-κN,S)}2] (3) (ppy=(2-phenylpyridinato-C2,N)) was prepared via the reaction of chloro-bridged dimer [{Pt(ppy)Cl}2] with 4,6-dimethylpyrimidine-2(1H)-thione (C6H8N2S) in the presence of t-BuOK. The complex holds dinuclear frameworks with short Pt(II)···Pt(II) distance (2.8877(3) Å), and exhibit red intense luminescence from the triplet metal-metal-to-ligand charge-transfer at 697 nm in CH2Cl2 solution and at 649 nm in solid state at RT. Single crystal XRD analysis reveals the metallophilic interactions Pt···Pt with significant covalent contribution in the structure of 3 which were studied by quasi-relativistic and relativistic DFT calculations (viz., M06/MWB60(Pt) and 6-311+G* (other atoms); M06/DZP-DKH levels of theory) and topological analysis of the electron density distribution within the framework of Bader’s theory (QTAIM method). Estimated strength of the Pt···Pt contact is 8.1–12.2 kcal/mol and it is mostly determined by crystal packing effects and weak attractive interactions between the adjacent metal centers due to overlapping of their dz2 and pz orbitals. An organic light-emitting diode based on this complex showed red electroluminescence with maximal luminance of 115 cd/m2 and current efficiency of 2.45 cd/A at this luminance.